Alicyclic esters having a musky smell

ABSTRACT

The invention relates to novel alicyclic esters, methods for the their preparation, their use as fragrances and also perfumed products and fragrance mixtures containing the compounds according to the invention.

FIELD OF THE INVENTION

The invention relates to novel alicyclic esters, methods for theirpreparation, their use as fragrances, and also perfumed products andfragrance mixtures containing the compounds according to the invention.

BACKGROUND OF THE INVENTION

Compounds with a musk fragrance are sought-after components in theperfume industry. They are characterized both by their property ofimparting an aura to perfume compositions and also by their ability toact as a fixer. Thus, musk fragrances are nowadays used in many perfumecompositions.

The synthesis of biodegradable compounds with a musk fragrance hasgained substantially in importance in recent years, since the syntheticmusk compounds of the nitro-aromatic and polycyclic series arepersistent and lipophilic, so that these compounds accumulate in aquaticfood chains and fatty tissue (H. Brunn, G. Rimkus, Ernährungs-Umschau1996, 43, 442 to 449; H. Brunn, G. Rimkus, Ernährungs-Umschau 1997, 44,4 to 9). In order to close the gap, macrocyclic musk fragrances that aresimilar to natural compounds and are characterized by a macrocyclic ringwith 13 to 17 C atoms, which has a ketone or an ester as functionalgroup, have been developed to an increasing extent.

Furthermore, U.S. Pat. No. 5,166,412 discloses compounds of type (II)

where R¹ is a C₁ to C₃ alkyl group and R² is an H or a methyl group.These compounds are characterized by a musk fragrance that is associatedwith ambergris and fruity aspects.

In addition, WO-A 00/14051 shows that esters of type (III)

where R¹ is a C₁ to C₄ alkyl or alkylene group and X is an oxygen, amethylene or ethylene group, also have a musk fragrance, the ambergrisand fruity aspects being further in the background.

The aim was now to find compounds which, on the one hand, have a muskfragrance and in addition, by means of further original fragranceaspects, expand the range of raw materials available for the compositionof perfumes.

SUMMARY OF THE INVENTION

The present invention relates to novel alicyclic esters of the formula(I)

whereR¹=CH₃, R³=H or CH₃ and R² and R⁴=H,R⁵ and R⁶—independently of one another—are H or CH₃ andY=—CR⁷R⁸OCOR⁹, where R⁷ and R⁸—independently of one another—are H or CH₃and

-   -   R⁹ is a branched or straight-chain C₁ to C₅ alkyl group or a        branched or straight-chain C₂ to C₅ alkylene group, or        R¹ and R²—independently of one another—are CH₃ or CH₂CH₃,        R³ and R⁴—independently of one another—are H or CH₃,        R⁵ and R⁶ together are oxygen and        Y=—CR⁷R⁸OCOR⁹ or R⁹, where R⁷, R⁸ and R⁹ have the abovementioned        meaning, or        R¹ and R²—independently of one another—are CH₃ or CH₂CH₃,        R³, R⁴, R⁵ and R⁶—independently of one another—are H or CH₃ and        Y=—CR⁷R⁸OCOR⁹, where R⁷, R⁸ and R⁹ have the abovementioned        meaning.

The present invention also relates to methods for the preparation of thecompounds according to the invention, their use as fragrances and alsoperfumed products and fragrance mixtures containing the compoundsaccording to the invention.

DETAILED DESCRIPTION

According to the invention branched or straight-chain C, to C₅ alkylgroups are understood to be, in particular, the alkyl radicals methyl,ethyl, n-propyl, iso-propyl, n-butyl, sec.-butyl, iso-butyl,tert.-butyl, n-pentyl, iso-pentyl and 3-methylbutyl. The alkyl radicalsmethyl, ethyl, n-propyl, iso-propyl, n-butyl, sec.-butyl, and iso-butylare preferred; the radicals methyl, ethyl and n-propyl are particularlypreferred.

According to the invention branched or straight-chain C₂ to C₅ alkylenegroups are understood to be in particular, the alkylene radicalsethenyl, methylethenyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl,1-methyl-1-propenyl, 1-butenyl, 3-butenyl, 1-methyl-1-butenyl,1-methyl-3-butenyl, 3-methyl-3-butenyl, 1-pentenyl, 2-pentenyl, and4-pentenyl. The alkylene radicals ethenyl, methylethenyl, 1-propenyl,2-propenyl, 2-methyl-1-propenyl, and 1-methyl-1-propenyl are preferred;the alkylene radicals ethenyl, methylethenyl, and 1-propenyl areparticularly preferred.

The novel alicyclic esters of the formula (I), according to theinvention, can be in the optically active form and also in the form ofarbitrary mixtures of their stereoisomers.

The alicyclic esters of the formula (I), according to the invention,achieve the stated objective; in addition to musk-like fragrance notesthat are of interest from the perfume standpoint, they are characterizedby interesting subsidiary notes. In this context it has been found,surprisingly, that the compounds in which R¹ and R² are methyl groupsare characterized by very fine woody aspects in addition to the musknote. The woody aspects retreat completely into the background if R¹ isa methyl group and R², R³, and R⁴ are hydrogen, so that these compoundsare characterized by flowery aspects, coupled with fruity accents.

Compounds that are particularly valuable from the sensory standpoint arecompounds of the formula (IV), which have a tertiary alkoxy group (R¹,R²=CH₃), since they also have woody aspects in addition to the musknote.

whereR³ and R⁴—independently of one another—are H or CH₃, where R³ andR⁴=methyl is preferredR⁵ and R⁶ together are hydrogen, andY=—CR⁷R⁸OCOR⁹ or R⁹, where R⁷, R⁸, and R⁹ have the abovementionedmeaning, where Y=methyl, ethyl or n-propyl, and also Y=—CR⁷R⁸OCOR⁹,where R⁷ and R⁸=H and R⁹=methyl, ethyl or n-propyl is preferred.

The compound of the formula (V), where the sweet, erogenous muskfragrance is associated with soft, woody aspects in a unique manner, isparticularly preferred, because of its attractive olfactory properties.

A further class of molecules that are very interesting from the sensorystandpoint and that also have flowery and fruity aspects in addition tothe musk note are represented in formula (VI).

whereR³=H or CH₃,R⁵ and R⁶—independently of one another—are H or CH₃, where R⁵, R⁶=methylis preferred, andY=—CR⁷R⁸OCOR⁹, where R⁷, R⁸, and R⁹ have the above-mentioned meaning,where R⁷ and R⁸=H and R⁹=methyl, ethyl or n-propyl is preferred.

The isomers of the formulae (VIIa) and (VIIb), where the erogenous,slightly ambergris-tinged musk fragrance is associated with intensiveflowery aspects in a unique manner, are particularly preferred, becauseof their attractive olfactory properties.

In this context according to the invention, the alicyclic esters of theformula (I) can be used as individual substances in a multiplicity ofproducts; particularly advantageous they can be combined with otherfragrances to give novel perfume compositions.

According to the invention, by using the alicyclic esters of formula (I)it is as a rule possible, even in low dosage, to achieve fine, erogenousmusk notes associated with woody or flowery aspects in the resultingperfume compositions, the overall fragrance impression being strikinglyharmonized, the aura being discernably increased and fixing, i.e. theadhesion of the perfume oil, being distinctly increased.

According to the invention, examples of fragrances with which thealicyclic esters of the formula (I) can advantageously be combined asprovided, for example, in K. Bauer, D. Garbe and H. Surburg, CommonFragrance and Flavor Materials, 3^(rd). Ed., Wiley-VCH, Weinheim 1997.

The following may be mentioned individually:

extracts from natural, raw materials, such as, essential oils,concretes, absolutes, resins, resinoids, balsams, tinctures, such as,for example, ambergris tincture; amyris oil; angelica seed oil; angelicaroot oil; aniseed oil; valerian oil; basil oil; wood moss absolute; bayoil; mugwort oil; benzoin resin; bergamot oil; beeswax absolute; birchtar oil; bitter almond oil; savory oil; bucho leaf oil; cabreuva oil;cade oil; calamus oil; camphor oil; cananga oil; cardamom oil;cascarilla oil; cassia oil; cassia absolute; castoreum absolute; cedarleaf oil; cedarwood oil; cistus oil; citronella oil; lemon oil; copaivabalsam; copaiva balsam oil; coriander oil; costus root oil; cumin oil;cypress oil; davana oil; dill herb oil; dill seed oil; eau de broutsabsolute; oakmoss absolute; elemi oil; tarragon oil; eucalyptuscitriodoura oil; eucalyptus oil; fennel oil; spruce needle oil; galbanumoil; galbanum resin; geranium oil; grapefruit oil; guaiac wood oil;gurjun balsam; gurjun balsam oil; helichrysum absolute; helichrysum oil;ginger oil; iris root absolute; iris root oil; jasmine absolute; calamusoil; camomile oil blue; Roman camomile oil; carrot seed oil; cascarillaoil; pine needle oil; spearmint oil; caraway oil; labdanum oil; labdanumabsolute; ladanum resin; lavandin absolute; lavandin oil; lavenderabsolute; lavender oil; lemongrass oil; lovage oil; distilled lime oil;pressed lime oil; linaloe oil; litsea cubeba oil; bayleaf oil; mace oil;marjoram oil; mandarin oil; massoi bark oil; mimosa absolute; musk seedoil; musk tincture; clary oil; nutmeg oil; myrrh absolute; myrrh oil;myrtle oil; clove leaf oil; clove blossom oil; neroli oil; olibanumabsolute; olibanum oil; opopanax oil; orange blossom absolute; orangeoil; origanum oil; palmarosa oil; patchouli oil; perilla oil; Peruvianbalsam oil; parsley leaf oil; parsley seed oil; petitgrain oil;peppermint oil; pepper oil; pimenta oil; pine oil; pennyroyal oil; roseabsolute; rosewood oil; rose oil; rosemary oil; Dalmation sage oil;Spanish sage oil; sandalwood oil; celery seed oil; spike lavender oil;Japanese anise oil; styrax oil; tagetes oil; fir needle oil; tea treeoil; turpentine oil; thyme oil; Tolu balsam; tonka absolute; tuberoseabsolute; vanilla extract; violet leaf absolute; verbena oil; vetiveroil; juniper oil; wine lees oil; absinthe oil; wintergreen oil; ylangoil; hyssop oil; civet absolute; cinnamon leaf oil; cinnamon bark oil;and fractions thereof or constituents isolated therefrom;

individual fragrances from the group comprising the hydrocarbons, suchas, for example, 3-carene; α-pinene; β-pinene; α-terpinene; γ-terpinene;p-cymene; bisabolene; camphene; caryophyllene; cedrene; famesene;limonene; longifolene; myrcene; ocimene; valencene;(E,Z)-1,3,5-undecatriene;

the aliphatic alcohols, such as, for example, hexanol; octanol;3-octanol; 2,6-dimethylheptanol; 2-methylheptanol, 2-methyloctanol;(E)-2-hexenol; (E)- and (Z)-3-hexenol; 1-octen-3-ol; mixture of3,4,5,6,6-pentamethyl-3/4-hepten-2-ol and3,5,6,6-tetramethyl-4-methyleneheptan-2-ol; (E,Z)-2,6-nonadienol;3,7-dimethyl-7-methoxyoctan-2-ol; 9-decenol; 10-undecenol;4-methyl-3-decen-5-ol; the aliphatic aldehydes and the1,4-dioxacycloalken-2-ones thereof, such as, for example, hexanal;heptanal; octanal; nonanal; decanal; undecanal; dodecanal; tridecanal;2-methyloctanal; 2-methylnonanal; (E)-2-hexenal; (Z)-4-heptenal;2,6-dimethyl-5-heptenal; 10-undecenal; (E)-4-decenal; 2-dodecenal;2,6,10-trimethyl-5,9-undecadienal; heptanal diethyl acetal;1,1-dimethoxy-2,2,5-trimethyl-4-hexene; and citronellyloxyacetaldehyde;

the aliphatic ketones and oximes thereof, such as, for example,2-heptanone; 2-octanone; 3-octanone; 2-nonanone; 5-methyl-3-heptanone;5-methyl-3-heptanone oxime; 2,4,4,7-tetramethyl-6-octen-3-one; thealiphatic sulphur-containing compounds, such as, for example,3-methylthiohexanol; 3-methylthiohexyl acetate; 3-mercaptohexanol;3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexylacetate; and 1-menthene-8-thiol;

the aliphatic nitriles, such as, for example, 2-nonenoic acid nitrile;2-tridecenoic acid nitrile; 2,12-tridecenoic acid nitrile;3,7-dimethyl-2,6-octadienoic acid nitrile; and 3,7-dimethyl-6-octenoicacid nitrile;

the aliphatic carboxylic acids and esters thereof, such as, for example,(E)- and (Z)-3-hexenyl formate; ethyl acetoacetate; isoamyl acetate;hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate;(E)-2-hexenyl acetate; (E)- and (Z)-3-hexenyl acetate; octyl acetate;3-octyl acetate; 1-octen-3-yl acetate; ethyl butyrate; butyl butyrate,isoamyl butyrate; hexyl butyrate; (E)- and (Z)-3-hexenyl isobutyrate;hexyl crotonate; ethyl isovalerate; ethyl 2-methylpentanoate; ethylhexanoate; allyl hexanoate; ethyl heptanoate; allyl heptanoate; ethyloctanoate; ethyl (E,Z)-2,4-decadienoate; methyl 2-octynoate; methyl2-nonynoate; allyl 2-isoamyloxyacetate; and methyl3,7-dimethyl-2,6-octadienoate;

the acyclic terpene alcohols, such as, for example, citronellol;geraniol; nerol; linalool; lavandulol; nerolidol; farnesol;tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7-octen-2-ol;2,6-dimethyloctan-2-ol; 2-methyl-6-methylene-7-octen-2-ol;2,6-dimethyl-5,7-octadien-2-ol; 2,6-dimethyl-3,5-octadien-2-ol;3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-1,5,7-octatrien-3-ol;2,6-dimethyl-2,5,7-octatrien-1-ol; and formates, acetates, propionates,isobutyrates, butyrates, isovalerates, pentanoates, hexanoates,crotonates, tiglinates, and 3-methyl-2-butenoates thereof;

the acyclic terpene aldehydes and ketones, such as, for example,geranial; Neral; cirtonellal; 7-hydroxy-3,7-dimethyloctanal;7-methoxy-3,7-dimethyl-octanal; 2,6,10-trimethyl-9-undecenal;geranylacetone; and the dimethyl and diethyl acetals of geranial, Neral,and 7-hydroxy-3,7-dimethyloctanal;

the cyclic terpene alcohols, such as, for example, menthol; isopulegol;alpha-terpineol; terpineol-4; menthan-8-ol; menthan-1-ol; menthan-7-ol;bomeol; isoborneol; linalool oxide; nopol; cedrol; ambrinol; vetiverol;guaiol; and formates, acetates, propionates, isobutyrates, butyrates,isovalerates, pentanoates, hexanoates, crotonates, tiglinates, and3-methyl-2-butenoates thereof;

the cyclic terpene aldehydes and ketones, such as, for example,menthone; isomenthone; 8-mercaptomenthan-3-one; carvone; camphor;fenchone; alpha-ionone; beta-ionone; alpha-n-methylionone;beta-n-methylionone; alpha-isomethylionone; beta-isomethylionone;alpha-irone; alpha-damascone; beta-damascone; beta-damascenone;delta-damascone; gamma-damascone;1-(2,4,4-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one;1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-methanonaphthalen-8(5H)-one;nootkatone; dihydronootkatone; alpha-sinensal; beta-sinensal, andacetylated cedarwood oil (methyl cedryl ketone);

the cyclic alcohols, such as, for example, 4-tert-butylcyclohexanol;3,3,5-trimethylcyclohexanol; 3-isocamphylcyclohexanol; and2,6,9-trimethyl-Z2,Z5,E9-cyclo-dodecatrien-1-ol and2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol;

the cycloaliphatic alcohols, such as, for example,alpha-3,3-trimethyl-cyclohexyl-methanol;2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butanol;2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol;2-ethyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol;3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-pentan-2-ol;3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol;3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol;1-(2,2,6-trimethylcyclohexyl)pentan-3-ol, and1-(2,2,6-trimethylcyclo-hexyl)hexan-3-ol;

the cyclic and cycloaliphatic ethers, such as, for example, cineole;cedryl methyl ether; cyclododecyl methyl ether; (ethoxymethoxy)cyclododecane; alpha-cedrene epoxide;3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan;3a-ethyl-6,6,9a-trimethyldodecahydronaphtho[2,1b]furan;1,5,9-trimethyl-13-oxabicyclo[10.1.0]trideca-4,8-diene; and rose oxideand2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-dioxane;

the cyclic ketones, such as, for example, 4-tert-butylcyclohexanone;2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone;2-pentylcyclo-pentanone; 2-hydroxy-3-methyl-2-cyclopenten-1-one;3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one;3-methyl-2-pentyl-2-cyclopenten-1-one; 3-methyl-4-cyclopentadecenone;3-methyl-5-cyclopentadecenone; 3-methylcyclopentadecanone;4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone;4-tert-pentylcyclohexanone; 5-cyclohexadecen-1-one;6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone;5-cyclohexadecen-1-one; 8-cyclohexadecen-1-one; 9-cycloheptadecen-1-oneand cyclo-pentadecanone;

the cycloaliphatic aldehydes, such as, for example,2,4-dimethyl-3-cyclo-hexenecarbaldehyde;2-methyl-4-(2,2,6-trimethyl-cyclohexen-1-yl)-2-butenal;4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde, and4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarbaldehyde;

the cycloaliphatic ketones, such as, for example,1-(3,3-dimethylcyclo-hexyl)-4-penten-1-one;1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one;2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphthalenyl methylketone; methyl 2,6,10-trimethyl-2,5,9-cyclododecatrienyl ketone, andtert-butyl 2,4-dimethyl-3-cyclohexen-1-yl ketone;

the esters of cyclic alcohols, such as, for example,2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate;2-tert-pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate;decahydro-2-naphthyl acetate; 3-pentyltetra-hydro-2H-pyran-4-yl acetate;decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate;4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl acetate;4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl propionate;4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl isobutyrate, and4,7-methanooctahydro-5 or 6-indenyl acetate;

the esters of cycloaliphatic carboxylic acids, such as, for example,allyl 3-cyclohexylpropionate; allyl cyclohexyloxyacetate; methyldihydrojasmonate; methyl jasmonate; methyl2-hexyl-3-oxocyclopentanecarboxylate; ethyl2-ethyl-6,6-dimethyl-2-cyclo-hexenecarboxylate; ethyl2,3,6,6-tetramethyl-2-cyclohexenecarboxylate, and ethyl2-methyl-1,3-dioxolane-2-acetate;

the aromatic hydrocarbons, such as, for example, styrene anddiphenylmethane;

the araliphatic alcohols, such as, for example, benzyl alcohol;1-phenylethyl alcohol; 2-phenylethyl alcohol; 3-phenylpropanol;2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol;2,2-dimethyl-3-(3-methyl-phenyl)propanol; 1,1-dimethyl-2-phenylethylalcohol; 1,1-dimethyl-3-phenylpropanol;1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpentanol;3-methyl-5-phenylpentanol; 3-phenyl-2-propen-1-ol; 4-methoxybenzylalcohol, and 1-(4-isopropylphenyl) ethanol;

the esters of araliphatic alcohols and aliphatic carboxylic acids, suchas, for example, benzyl acetate; benzyl propionate; benzyl isobutyrate;benzyl isovalerate; 2-phenylethyl acetate; 2-phenylethyl propionate;2-phenylethyl isobutyrate; 2-phenylethyl isovalerate; 1-phenylethylacetate; alpha-trichloromethylbenzyl acetate;alpha,alpha-dimethylphenylethyl acetate; alpha,alpha-dimethylphenylethylbutyrate; cinnamyl acetate; 2-phenoxyethyl isobutyrate; 4-methoxybenzylacetate; the araliphatic ethers, such as, for example, 2-phenylethylmethyl ether; 2-phenylethyl isoamyl ether; 2-phenylethyl 1-ethoxyethylether; phenylacetaldehyde dimethyl acetal; phenylacetaldehyde diethylacetal; hydratropic aldehyde dimethyl acetal; phenylacetaldehydeglycerol acetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxane;4,4a,5,9b-tetrahydroindeno[1,2-d]-m-dioxin; and4,4a,5,9b-tetrahydro-2,4-dimethylindeno[1,2-d]-m-dioxin;

the aromatic and araliphatic aldehydes, such as, for example,benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; hydratropicaldehyde; 4-methylbenzaldehyde; 4-methylphenylacetaldehyde;3-(4-ethylphenyl)-2,2-dimethylpropanal;2-methyl-3-(4-isopropyl-phenyl)propanal;2-methyl-3-(4-tert-butylphenyl)propanal;3-(4-tert-butyl-phenyl)propanal; cinnamaldehyde;alpha-butylcinnamaldehyde; alpha-amylcinnamaldehyde;alpha-hexylcinnamaldehyde; 3-methyl-5-phenylpentanal;4-methoxybenzaldehyde; 4-hydroxy-3-methoxy-benzaldehyde;4-hydroxy-3-ethoxybenzaldehyde; 3,4-methylenedioxy-benzaldehyde;3,4-dimethoxybenzaldehyde; 2-methyl-3-(4-methoxy-phenyl)propanal and2-methyl-3-(4-methylenedioxyphenyl)propanal;

the aromatic and araliphatic ketones, such as, for example,acetophenone; 4-methylacetophenone; 4-methoxyacetophenone;4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone;4-(4-hydroxyphenyl)-2-butanone; 1-(2-naphthalenyl)ethanone;benzophenone; 1,1,2,3,3,6-hexamethyl-5-indanyl methyl ketone;6-tert-butyl-1,1-dimethyl-4-indanyl methyl ketone; and1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5-indenyl]ethanoneand5′,6′,7′,8′-tetrahydro-3′,5′,5′,6′,8′,8′-hexamethyl-2-acetonaphthone;

the aromatic and araliphatic carboxylic acids and esters thereof, suchas, for example, benzoic acid; phenylacetic acid; methyl benzoate; ethylbenzoate; hexyl benzoate; benzyl benzoate; methyl phenylacetate; ethylphenylacetate; geranyl phenylacetate; phenylethyl phenylacetate; methylcinnamate; ethyl cinnamate; benzyl cinnamate; phenylethyl cinnamate;cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isoamylsalicylate; hexyl salicylate; cyclohexyl salicylate; cis-3-hexenylsalicylate; benzyl salicylate; phenylethyl salicylate; methyl2,4-dihydroxy-3,6-dimethylbenzoate; ethyl 3-phenylglycidate and ethyl3-methyl-3-phenylglycidate;

the nitrogen-containing aromatic compounds, such as, for example,2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene;3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone; cinnamonitrile;5-phenyl-3-methyl-2-pentenoic acid nitrile; 5-phenyl-3-methylpentanoicacid nitrile; methyl anthranilate; methyl N-methylanthranilate; Schiffsbases of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal;2-methyl-3-(4-tert-butylphenyl)propanal or2,4-dimethyl-3-cyclohexenecarbaldehyde; 6-isopropylquinoline;6-isobutylquinoline; 6-sec-butylquinoline; indole; scatole; and2-methoxy-3-isopropylpyrazine and 2-isobutyl-3-methoxypyrazine;

the phenols, phenyl ethers and phenyl esters, such as, for example,estragole; anethole; eugenol; eugenyl methyl ether; isoeugenol;isoeugenyl methyl ether; thymol; carvacrol; diphenyl ether;beta-naphthyl methyl ether; beta-naphthyl ethyl ether; beta-naphthylisobutyl ether; 1,4-dimethoxybenzene; eugenyl acetate;2-methoxy-4-methylphenol; and 2-ethoxy-5-(1-propenyl)phenol and p-cresylphenylacetate;

the heterocyclic compounds, such as, for example,2,5-dimethyl-4-hydroxy-2H-furan-3-one;2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one;3-hydroxy-2-methyl-4H-pyran-4-one and 2-ethyl-3-hydroxy-4H-pyran-4-one;

the lactones, such as, for example, 1,4-octanolide;3-methyl-1,4-octanolide; 1,4-nonanolide; 1,4-decanolide;8-decen-1,4-olide; 1,4-undecanolide; 1,4-dodecanolide; 1,5-decanolide;1,5-dodecanolide; 1,15-pentadecanolide; cis- andtrans-11-pentadecen-1,15-olide; cis- and trans-12-pentadecen-1,15-olide;1,16-hexadecanolide; 9-hexadecen-1,16-olide; 10-oxa-1,16-hexadecanolide;11-oxa-1,16-hexadecanolide; 12-oxa-1,16-hexadecanolide; ethylene1,12-dodecanedioate; ethylene 1,13-tridecanedioate; coumarin;2,3-dihydrocoumarin and octahydrocoumarin.

According to the invention, the perfume oils containing the alicyclicesters of the formula (I) according to the invention can be used inliquid form, undiluted or diluted, with a solvent for perfumingpurposes. Suitable solvents for this purpose are, for example, ethanol,isopropanol, diethylene glycol monoethyl ether, glycerol, propyleneglycol, 1,2-butylene glycol, dipropylene glycol, diethyl phthalate,triethyl citrate, isopropyl myristate, etc.

Furthermore, according to the invention, the perfume oils containing thealicyclic esters of the formula (I) can be adsorbed on a carrier, whichserves both for fine dispersion of the fragrances in the product and,also, for controlled release during use. Such carriers can be porousinorganic materials, such as light sulphate, silica gels, zeolites,gypsums, clays, clay granules, gas concrete, etc. or organic materials,such as woods and cellulose-based substances.

According to the invention, the perfume oils containing the alicyclicesters of the formula (I) according to the invention can also bemicroencapsulated, spray-dried, in the form of inclusion complexes or inthe form of extrusion products and can be added in this form to theproduct to be perfumed.

The properties of the perfume oils modified in this way can optionallybe further optimised by so-called, “coating” with suitable materialswith regard to a more targeted fragrance release, for which purpose waxyplastics, such as, for example, polyvinyl alcohol, are preferably used.

The microencapsulation of the perfume oils can, for example, be carriedout by the so-called coacervation method, with the aid of capsulematerials made from, for example, polyurethane-like substances or softgelatine. The spray-dried perfume oils can, for example, be prepared byspray drying an emulsion or dispersion containing the perfume oil, wherethe carriers used can be modified starches, proteins, dextrin, andvegetable gums. Inclusion complexes can be prepared, for example, byintroducing dispersions of the perfume oil and cyclodextrins or ureaderivatives into a suitable solvent, e.g. water. Extrusion products canbe obtained by melting the perfume oils with a suitable waxy substanceand by extrusion with subsequent solidification, optionally, in asuitable solvent, e.g. isopropanol.

According to the invention, in perfume compositions, the amount of thealicyclic esters of the formula (I) that is used is 0.05 to 50% (m/m),preferably 0.5 to 20% (m/m), based on the total perfume oil.

According to the invention, the perfume oils containing the alicyclicesters of the formula (I) according to the invention can be used inconcentrated form, in solutions, or in a modified form described abovefor the preparation of, for example, perfume extracts, eau de parfums,eau de toilettes, aftershaves, eau de colognes, pre-shave products,splash colognes, perfumed freshening wipes and for perfuming acid,alkaline, and neutral cleaning agents, such as, for example, floorcleaners, window cleaners, washing-up liquids, bath and sanitaryequipment cleaners, scouring agents, solid and liquid WC cleaners,carpet cleaners in powder and foam form, liquid detergents, powderdetergents, laundry pre-treatment agents, such as bleaching agents,softeners and stain removers, fabric conditioners, laundry soaps,laundry tablets, disinfectants, surface disinfectants and air freshenersin liquid or gel form or applied to a solid support, aerosol sprays,waxes and polishes, such as furniture polishes, floor waxes, cream shoepolishes and personal hygiene agents, such as, for example, solid andliquid soaps, shower gels, shampoos, shaving soaps, shaving foams, bathoils, cosmetic emulsions of the oil-in-water, of the water-in-oil and ofthe water-in-oil-in-water type, such as, for example, skin creams andlotions, face creams and lotions, sun protection creams and lotions,after-sun creams and lotions, hand creams and lotions, foot creams andlotions, depilatory creams and lotions, after-shave creams and lotions,bronzing creams and lotions, hair care products, such as, for example,hair sprays, hair gels, hair lotions, hair rinses, permanent andsemi-permanent hair dyes, hair shaping agents such as cold permanentwaves, and hair smoothing agents, hair tonics, hair creams and lotions,deodorants and antiperspirants, such as, for example, under-arm sprays,roll-ons, deodorants sticks, deodorant creams or decorative cosmeticproducts, such as, for example, eye shadows, nail varnishes, make-ups,lipsticks and mascara, and also of candles, lamp oils, fumigatingsticks, insecticides, repellents, and propellants.

According to the invention, the novel alicyclic esters can, for example,be prepared in the following way:

The preparation of the alicyclic esters of the formula (1), according tothe invention, in which:

R¹ and R²—independently of one another—are CH₃ or CH₂CH₃,

R³ and R⁴—independently of one another—are H or CH₃,

R⁵ and R⁶ together are oxygen, and

Y is —CR⁷R⁸OCOR⁹, where R⁷ and R⁸—independently of one another—are H orCH₃ and

R⁹ is a branched or straight-chain C₁ to C₅ alkyl group or a branched orstraight-chain C₂ to C₅ alkylene group

can be carried out in accordance with synthesis route A.

In synthesis route A, the substituted cyclohexylalkanol (VIII) isesterified with the carboxylic acid (IX), which is obtainable byreaction of the corresponding α-hydroxycarboxylic acid with thecorresponding acid chloride (Thayer, F. K., Organic Synthesis Col. Vol.1 (1932), p. 12). The esterification can be carried out by methods wellknown to those skilled in the art, for example, by heating the twoeducts in a water separator in the presence of an entraining agent (forexample toluene or cyclohexane) with the addition of 0.01% (mol) to 10%(mol), preferably 0.1% (mol) to 5% (mol), of an acid, preferablyp-toluenesulphonic acid or sulphuric acid, or by the so-called Steglichmethod, where the esterification is carried out with the addition ofdicyclohexylcarbodiimide and 0.02% (mol) to 20% (mol), preferably 0.5%(mol) to 10% (mol) 4-dimethylaminopyridine.

The preparation of the alicyclic esters of the formula (I) according tothe invention in which

R¹ and R²—independently of one another—are CH₃ or CH₂CH₃,

R³ and R⁴—independently of one another—are H or CH₃,

R⁵ and R⁶ together are oxygen and

Y=R⁹ and R⁹ has the abovementioned meaning,

can be carried out in accordance with synthesis route B.

In synthesis route B, the substituted cyclohexylalkanol (VIII) isesterified by the methods well known to those skilled in the art. Here,the esterification can take place by heating the substitutedcyclohexylalkanol (VIII) and the corresponding carboxylic acid in awater separator, in the presence of an entraining agent (for example,toluene or cyclohexane) with the addition of 0.01% (mol) to 10% (mol),preferably 0.1% (mol) to 5% (mol) of an acid, preferably,p-toluenesulphonic acid or sulphuric acid, or by reaction of thesubstituted cyclohexylalkanol (VIII) with the corresponding carboxylicacid anhydride in the presence of triethylamine and 0.5% (mol) to 50%(mol), preferably 1.0% (mol) to 30% (mol), 4-dimethyl-aminopyridine.

The preparation of the alicyclic esters of the formula (I) according tothe invention in which

R¹=CH₃, R³=H or CH₃ and R² and R⁴=H,

R⁵ and R⁶—independently of one another—are H or CH₃ and

Y=—CR⁷R⁸OCOR⁹, where R⁷, R⁸ and R⁹ have the above-mentioned meaning, or

R¹ and R²—independently of one another—are CH₃ or CH₂CH₃,

R³, R⁴, R⁵ and R⁶—independently of one another—are H or CH₃ and

Y=—CR⁷R⁸OCOR⁹, where R⁷, R⁸ and R⁹ have the above-mentioned meaning,

can be carried out in accordance with synthesis route C.

In step 1 of synthesis route C, the epoxide (X) is nucleophilicallyopened using the substituted cyclohexylalkanol (VIII). If anasymmetrically substituted epoxide is used in the reaction, theresulting alcohol (XI) can be obtained as a mixture of two regioisomers.This reaction can, for example, be carried out with the addition of0.02% (mol) to 20% (mol), preferably 0.5% (mol) to 10% (mol), of a Lewisacid; preferred Lewis acids contain a boron atom; BF₃—OEt₂ isparticularly preferred. The resulting alcohol (XI) is esterified bymethods well known to those skilled in the art. Here, the esterificationcan take place by heating the alcohol (XI) and the correspondingcarboxylic acid in a water separator in the presence of an entrainingagent (for example, toluene or cyclohexane) with the addition of 0.01%(mol) to 10% (mol), preferably 0.1% (mol) to 5% (mol) of an acid,preferably p-toluenesulphonic acid or sulphuric acid, or by reaction ofthe alcohol (XI) with the corresponding carboxylic acid anhydride in thepresence of triethylamine and 0.5% (mol) to 50% (mol), preferably, 1.0%(mol) to 30% (mol), 4-dimethylaminopyridine.

The following equations can illustrate the methods according to theinvention:

Alternatively, the alicyclic esters of the formula (I), according to theinvention, in which

R¹ and R²—independently of one another—are CH₃ or CH₂CH₃,

R³ and R⁴—independently of one another—are H or CH₃,

R⁵ and R⁶ together are oxygen and

Y=—CR⁷R⁸OCOR⁹, where R⁷, R⁸ and R⁹ have the above-mentioned meaning,

can be prepared in accordance with synthesis route D.

In step 1 of synthesis route D, the substituted cyclohexylalkanol (VIII)is esterified by methods well known to those skilled in the art. Here,the esterification can be carried out by heating the substitutedcyclohexylalkanol (VIII) and the corresponding carboxylic acid, where Xis an OH group or a halogen, preferably, an OH group or a chlorine atom,in a water separator in the presence of an entraining agent (forexample, toluene or cyclohexane) with the addition of 0.01% (mol) to 10%(mol), preferably 0.1% (mol) to 5% (mol), of an acid, preferablyp-toluenesulphonic acid or sulphuric acid. Furthermore, the reaction ofthe substituted cyclohexylalkanol (VIII) with the correspondingcarboxylic acid anhydride, where X is an OH group or a halogen,preferably, an OH group or a chlorine atom, can take place in pyridine.

In step 2, if X=OH, the ester (XII) is esterified with the correspondingcarboxylic acid (Z=H). The reaction can be carried out, for example, ina water separator in the presence of an entraining agent (for example,toluene or cyclohexane) with the addition of 0.01% (mol) to 10% (mol),preferably, 0.1% (mol) to 5% (mol), of an acid. Preferred acids arep-toluenesulphonic acid or sulphuric acid. Furthermore, the reaction ofthe ester (XII) where X=OH with the corresponding carboxylic acidanhydride (Z=—C(O)R⁹) can take place in the presence of triethylamineand 0.5% (mol) to 50% (mol), preferably 1.0% (mol) to 30% (mol),4-dimethyl-aminopyridine.

If X=halogen, and, preferably, X=chlorine, the ester (XII) can, on theone hand, be reacted with an alkali metal salt of a carboxylic acid(Z=alkali metal; sodium and potassium are preferred) in the presence ofan alkali metal salt, preferably, sodium bromide, or in the presence ofthe corresponding carboxylic acid anhydride. On the other hand, theester (XII) where X=halogen and, preferably, X=chlorine can be reactedwith a carboxylic acid (Z=H) in the presence of a base, preferably,potassium carbonate.

The following examples illustrate the invention:

EXAMPLE 1 2-(1-cyclohexylethoxy)-2-methylpropyl propionate

2-(1-cyclohexylethoxy)-2-methyl-1-propanol: BF₃—OEt₂ (2.0 ml) is addeddropwise to a solution of 1-cyclohexylethanol (16.6 g, 127.0 mmol) andisobutylene oxide (2.9 g, 40.0 mmol) in cyclohexane (20 ml) that hasbeen cooled to 0° C. The reaction mixture is now stirred at 0° C. for afurther 30 minutes, and further, BF₃—OEt₂ (2.0 ml) is then added. Aftera further 3 hours at 0° C., the cooling is removed and the reactionsolution is washed once with 1 M NaOH (15 ml). The organic phase isdried over Na₂SO₄, filtered off and freed from solvent in a rotaryevaporator. The 1-cyclohexylethanol that has not completely reacted isremoved from the crude product; thus, obtained by means of bulb tubedistillation (BTD) and 5.3 g crude2-(1-cyclohexylethoxy)-2-methyl-1-propanol is obtained which has a GCcontent of 75% and can be used in the next reaction without furtherpurification.

2-(1-cyclohexylethoxy)-2-methylpropyl propionate: triethylamine (1.6 g,15 mmol) and 4-dimethylaminopyridine (0.13 g, 1.0 mmol) are addedsuccessively to a solution of 2-(1-cyclohexylethoxy)-2-methyl-1-propanol(GC purity: 75%; crude product from the first stage) (1.46 g, 5.5 mmol)and propionic anhydride (2.0 g, 15 mmol). After stirring for 1 hour atroom temperature, the reaction solution is diluted with ether (100 ml),and the organic phase is washed twice with 2 M HCl and twice withsaturated NaHCO₃ solution. The combined organic phases are dried overNa₂SO₄, filtered off, and freed from solvent in a rotary evaporator.After flash chromatography (cyclohexane/EtOAc=45:1, R_(f)=0.25) and bulbtube distillation (BTD: 137° C., 0.5 mbar), 930 mg (70%)2-(1-cyclohexylethoxy)-2-methylpropyl propionate is obtained as acolorless oil.

Odour: strongly musk, erogenous, ambergris-tinged, flowery

¹H-NMR (200 MHz, CDCl₃): δ (ppm)=0.80–1.35 (m, 6H), 1.06 (d, J=6.1 Hz,3H), 1.16 (t, J=7.5 Hz, 3H), 1.18 (s, 6H), 1.55–1.85 (m, 5H), 2.37 (q,J=7.5 Hz, 2H), 3.40 (quin, J=6.1 Hz, 1H), 3.95 (s, 2H).

¹³C-NMR (50 MHz, CDCl₃): δ (ppm)=9.1, 19.7, 23.8, 24.0, 26.5, 26.6,26.7, 27.7, 28.5, 29.5, 44.9, 70.3, 71.6, 73.7, and 174.3.

The following compounds of Examples 2 and 3 were prepared analogously tothe methods described under Example 1, except that the esterificationwas carried out with acetic anhydride (Example 2) or isobutyricanhydride (Example 3). Thus, only the spectroscopic data are given atthis point:

EXAMPLE 2 2-(1-cyclohexylethoxy)-2-methylpropyl acetate

Odour: musk, flowery, and fruity.

BTD: 140° C., 0.6 mbar.

¹H-NMR (200 MHz, CDCl₃): δ (ppm)=0.80–1.35 (m, 6H), 1.06 (d, J=6.2 Hz,3H), 1.18 (s, 6H), 1.56–1.88 (m, 5H), 2.08 (s, 3H), 3.40 (quin, J=6.2Hz, 1H), 3.92 (d, J=11.2 Hz, 1H), and 3.95 (d, J=11.2 Hz, 1H).

¹³C-NMR (50 MHz, CDCl₃): δ (ppm)=19.7, 20.9, 23.7, 24.0, 26.4, 26.5,26.6, 28.4, 29.4, 44.8, 70.4, 71.6, 73.6, and 170.8.

EXAMPLE 3 2-(1-cyclohexylethoxy)-2-methylpropyl isobutyrate

Odour: musk, erogenous, and flowery.

BTD: 164° C., 0.5 mbar.

¹H-NMR (200 MHz, CDCl₃): δ (ppm)=0.80–1.30 (m, 6H), 1.06 (d, J=6.2 Hz,3H), 1.18 (s, 6H), 1.19 (d, J=7.0 Hz, 6H), 1.60–1.90 (m, 5H), 2.58 (hep,J=7.0 Hz, 1H), 3.40 (quin, J=6.2 Hz, 1H), and 3.93 (s, 2H).

¹³C-NMR (50 MHz, CDCl₃): δ (ppm)=18.9 (2C), 19.7, 23.7, 24.0, 26.4,26.5, 26.6, 28.4, 29.4, 34.1, 44.8, 70.1, 71.6, 73.7, and 176.7.

The following compounds of Examples 4 and 5 were prepared analogously tothe methods described under Example 1, except that the alcohol componentused was 1-cyclohexyl-1-propanol, which can be prepared fromcyclohexylmagnesium chloride and propanal by a Grignard reaction,instead of 1-cyclohexyl-1-ethanol. The esterification was carried outwith acetic anhydride (Example 4) or propionic anhydride (Example 5).Thus, only the spectroscopic data are given at this point:

EXAMPLE 4 2-(1-cyclohexylpropoxy)-2-methylpropyl acetate

Odour: weakly musk, flowery, and fruity.

BTD: 161° C., 0.75 mbar.

¹H-NMR (200 MHz, CDCl₃): δ (ppm)=0.80–1.30 (m, 6H), 0.86 (t, J=7.4 Hz,3H), 1.19 (s, 6H), 1.35–1.50 (m, 2H), 1.55–1.80 (m, 5H), 2.08 (s, 3H),3.24 (q, J=5.4 Hz, 1H), and 3.95 (s, 2H).

¹³C-NMR (50 MHz, CDCl₃): δ (ppm)=9.5, 20.9, 24.0, 24.1, 24.7, 26.6 (2C),26.7, 28.5, 29.2, 41.5, 70.8, 73.5, 76.7, and 170.9.

EXAMPLE 5 2-(1-cyclohexylpropoxy)-2-methylpropyl propionate

Odour: musk, flowery, and fruity.

BTD: 155° C., 0.55 mbar.

¹H-NMR (200 MHz, CDCl₃): δ (ppm)=0.86 (t, 7.4 Hz, 3H), 0.90–1.25 (m,6H), 1.16 (t, J=7.6 Hz, 3H), 1.18 (s, 6H), 1.30–1.55 (m, 2H), 1.55–1.85(m, 5H), 2.36 (q, J=7.6 Hz, 2H), 3.24 (q, J=5.3 Hz, 1H), and 3.94 (s,2H).

¹³C-NMR (50 MHz, CDCl₃): δ (ppm)=9.1, 9.5, 24.0, 24.1, 24.7, 26.6 (2C),26.7, 27.7, 28.6, 29.2, 41.5, 70.6, 73.7, 76.7, and 174.2.

The following compounds of Examples 6 and 7 were prepared analogously tothe methods described under Example 1, except that the alcohol componentused was 2-cyclohexyl-2-propanol, which can be prepared fromcyclohexylmagnesium chloride and acetone by a Grignard reaction, insteadof 1-cyclohexyl-1-ethanol. Furthermore, propylene oxide was used insteadof isobutylene oxide. The esterification was carried out with aceticanhydride (Example 6) or propionic anhydride (Example 7). Thus, only thespectroscopic data are given at this point:

EXAMPLE 6 2-(1-cyclohexyl-1-methylethoxy) propylacetate/2-(1-cyclohexyl-1-methylethoxy)-1-methylethyl acetate

Regioisomer ratio=1:3

Odour: weakly musk, and fruity.

BTD: 142° C., 0.6 mbar.

The spectroscopic data relate to the main isomer:

¹H-NMR (200 MHz, CDCl₃): δ (ppm)=0.9–1.25 (m, 6H), 1.06 (s, 6H), 1.22(d, J=6.4 Hz, 3H), 1.70–1.85 (m, 5H), 2.03 (s, 3H), 3.28 (dd, J=9.7, 5.0Hz, 1H), 3.37 (dd, J=9.7, 5.8 Hz, 1H), 5.00 (ddq, J=5.0, 5.8, 6.4 Hz,1H).

¹³C-NMR (50 MHz, CDCl₃): δ (ppm)=16.9, 21.3, 22.5, 22.7, 26.7, 26.8,26.9, 27.4, 27.5, 46.4, 63.4, 70.3, 78.0, and 170.6.

EXAMPLE 7 2-(1-cyclohexyl-1-methylethoxy) propylpropionate/2-(1-cyclohexyl-1-methylethoxy)-1-methylethyl propionate

Regioisomer ratio=1:3

Odour: musk, and fruity.

BTD: 152° C., 0.72 mbar.

The spectroscopic data relate to the main isomer:

¹H-NMR (200 MHz, CDCl₃): δ (ppm)=0.88–1.24 (m, 6H), 1.06 (s, 6H), 1.13(t, J=7.6 Hz, 3H), 1.23 (d, J=6.4 Hz, 3H), 1.70–1.85 (m, 5H), 2.30 (q,J=7.6 Hz, 2H), 3.28 (dd, J=9.6, 5.1 Hz, 1H), 3.37 (dd, J=9.6, 5.9 Hz,1H), and 4.97 (ddq, J=5.1, 5.9, 6.4 Hz, 1H).

¹³C-NMR (50 MHz, CDCl₃): δ (ppm)=9.2, 17.0, 22.5, 22.7, 26.7, 26.8,26.9, 27.4, 27.5, 27.9, 46.5, 63.5, 70.1, 77.0, and 174.1.

The following compounds of Examples 8 and 9 were prepared analogously tothe methods described under Example 1, except that the alcohol componentused was 1-(3-methyl-cyclohexyl)-ethanol, which can be prepared byhydrogenation of 3-methylacetophenone, instead of1-cyclohexyl-1-ethanol. The esterification was carried out with aceticanhydride (Example 8) or propionic anhydride (Example 9). Thus, only thespectroscopic data are given at this point:

EXAMPLE 8 2-[1-(3-methyl-cyclohexyl)-ethoxy]-2-methylpropyl acetate

Odour: musk, flowery, and fruity.

BTD: 142° C., 0.75 mbar.

¹H-NMR (200 MHz, CDCl₃): δ (ppm)=0.55 (q, J=12.1 Hz, 1H), 0.72–0.86 (m,1H), 0.88 (d, J=6.6 Hz, 3H), 1.07 (d, J=6.1 Hz, 3H), 1.18 (s, 6H),1.20–1.40 (m, 4H), 1.60–1.82 (m, 4H), 2.08 (s, 3H), 3.40 (quin, J=6.1Hz, 1H), and 3.95 (d, J=11.2 Hz, 2H).

¹³C-NMR (50 MHz, CDCl₃): δ (ppm): 19.7, 20.9, 23.1, 23.8, 24.0, 26.2,28.0, 32.7, 35.3, 35.4, 44.9, 70.5, 71.6, 73.7, and 170.9.

EXAMPLE 9 2-[1-(3-methyl-cyclohexyl)-ethoxy]-2-methylpropyl propionate

Odour: strongly musk, flowery, and fruity.

BTD: 153° C., 0.75 mbar.

¹H-NMR (200 MHz, CDCl₃): δ (ppm)=0.55 (q, J=12.1 Hz, 1H), 0.72–0.86 (m,1H), 0.88 (d, J=6.6 Hz, 3H), 1.07 (d, J=6.1 Hz, 3H), 1.16 (t, J=7.6 Hz,3H), 1.18 (s, 6H), 1.20–1.40 (m, 4H), 1.60–1.82 (m, 4H), 2.37 (q, J=7.6Hz, 2H), 3.40 (quin, J=6.1 Hz, 1H), and 3.94 (d, J=11.2 Hz, 2H).

¹³C-NMR (50 MHz, CDCl₃): δ (Ppm): 9.1, 19.7, 23.0, 23.8, 24.1, 26.3,27.7, 29.0, 32.7, 35.4, 37.1, 44.9, 70.3, 71.6, 73.8, and 174.2.

EXAMPLE 10A 2-[1-(3,3-dimethylcyclohexyl)-1-methylethoxy]-2-oxoethylpropionate

(Propionyloxy) acetic acid: a solution consisting of propionyl chloride(64.7 g, 0.7 mol) and hydroxyacetic acid (19.0 g, 0.25 mol) is heated at40° C., until the hydroxyacetic acid has completely dissolved. Theexcess propionyl chloride is then distilled off and 35.6 g of crudeproduct containing 82% of (propionyloxy)acetic acid is obtained as acolorless liquid. The crude product can be used in the subsequentreaction without further purification.

2-[1-(3,3-dimethylcyclohexyl)-1-methylethoxy]-2-oxoethyl propionate:4-dimethyl-aminopyridine (122 mg, 1.0 mmol) and2-(3,3-dimethylcyclohexyl)-2-propanol (2.6 g, 15 mmol), [which isobtainable from methylmagnesium chloride and1-(3,3-dimethylcyclohexyl)-ethanone by a Grignard reaction] are addedsuccessively to a solution of 81% (propionyloxy) acetic acid (2.7 g,16.5 mmol) in CH₂Cl₂ (15 ml). The reaction solution is now cooled to 0°C. and dicyclohexylcarbodiimide (3.4 g, 16.5 mmol), dissolved in CH₂Cl₂(5 ml) is added. After 1 h at 0° C., the cooling is removed, and thereaction mixture is stirred for a further 16 h at room temperature. Theprecipitate that has precipitated is, then, filtered off, and thefiltrate is freed from solvent in a rotary evaporator. The resultingcrude product is taken up in n-pentane (20 ml) and the precipitate thatforms is again filtered off. The filtrate is also washed twice with 0.5M HCl and twice with saturated NaHCO₃ solution, and the organic phase isthen dried over Na₂SO₄, filtered off, and concentrated in a rotaryevaporator. After purification by flash chromatography(cyclohexane/EtOAc=10:1, R_(f)=0.23) and subsequent bulb tubedistillation (BTD: 221° C., 1.3 mbar), 3.1 g (73%)2-[1-(3,3-dimethylcyclohexyl)-1-methylethoxy]-2-oxoethyl propionate isobtained as a colorless liquid.

Odour: strongly musk, woody, and erogenous.

¹H-NMR (200 MHz, CDCl₃): δ (ppm)=0.80–1.40 (m, 4H), 0.88 (s, 3H), 0.92(s, 3H), 1.18 (t, J=7.6 Hz, 3H), 1.42 (d, J=0.6 Hz, 6H), 1.50–1.76 (m,4H), 2.03 (tt, J=12.4, 3.1 Hz, 1H), 2.44 (q, J=7.6 Hz, 2H), 4.46 (d,J=15.8 Hz, 1H), and 4.55 (d, J=15.8 Hz, 1H).

¹³C-NMR (50 MHz, CDCl₃): δ (ppm)=8.9, 22.2, 23.3 (2C), 24.5, 27.0, 27.1,30.7, 33.6, 39.0, 40.0, 42.0, 61.0, 87.4, 166.7, and 173.5.

EXAMPLE 10B

Alternatively to the methods in Example 10a,2-[1-(3,3-dimethylcyclohexyl)-1-methylethoxy]-2-oxoethyl propionate canbe prepared via the following two-stage synthesis route.

1-(3,3-dimethylcyclohexyl)-1-methylethyl chloroacetate: chloroaceticanhydride (213.7 g, 1.12 mol) is added in portions to a solution of2-(3,3-dimethylcyclohexyl)-2-propanol (127.7 g, 0.75 mol) in pyridine(175 ml), which has been cooled to 0° C., in such a way that thetemperature does not rise above 10° C. When the addition is complete,the reaction mixture is allowed to allowed to warm to room temperatureand stirred for a further 3 hours. The reaction mixture is then cooledto 0° C. again and water (500 ml) is added. The phases are separated,and the aqueous phase is extracted a further three times with ether (500ml). The combined organic phases are also washed twice with 1 M HCl,then dried, filtered off and freed from solvent in a rotary evaporator.Subsequent distillation (b.p. 103° C., 0.5 mbar) yields 152 g (82%)1-(3,3-dimethylcyclohexyl)-1-methylethyl chloroacetate as a colorlessliquid.

2-[1-(3,3-dimethylcyclohexyl)-1-methylethoxy]-2-oxoethyl propionate:K₂CO₃ (6.2 g, 45 mmol) and 1-(3,3-dimethylcyclohexyl)-1-methylethylchloroacetate (2,5 g, 10 mmol) are added successively to a solution ofpropionic acid (1.8 g, 30 mmol) in acetone (20 ml). After the suspensionhas been heated under reflux for 36 hours, it is allowed to cool andether (80 ml) and 10% K₂CO₃ solution (50 ml) are added. After phaseseparation has taken place, the aqueous phase is freed from residualacetone and the aqueous phase is also extracted twice with 50 ml diethylether. The combined organic phases are also washed once with water andonce with saturated NaCl solution, then dried, filtered off and freedfrom solvent in a rotary evaporator. After purification by flashchromatography (cyclohexane/EtOAc=10:1, R_(f)=0.23) and subsequent bulbtube distillation, (BTD: 215° C., 0.9 mbar) 2.1 g (78%)2-[1-(3,3-dimethylcyclohexyl)-1-methylethoxy]-2-oxoethyl propionate isobtained as a colorless liquid.

The odor and the spectroscopic data are identical to the data for thecompound that was prepared under Example 10a.

The following compounds were prepared analogously to the methodsdescribed under Example 8a (sic), except that in Example 9 (sic)acetyloxyacetic acid (which can be prepared from hydroxyacetic acid andacetyl chloride), in Example 10 (sic) isobutyryloxyacetic acid, (whichcan be prepared from hydroxyacetic acid and isobutyryl chloride) and inExample 11 (sic) butyryloxyacetic acid, (which can be prepared fromhydroxyacetic acid and butyryl chloride) is used in the esterification.Thus, only the spectroscopic data are given at this point:

EXAMPLE 11 2-[1-(3,3-dimethylcyclohexyl)-1-methylethoxy]-2-oxoethylacetate

Odour: strongly musk, woody, and animal.

BTD: 192° C., 0.35 mbar.

¹H-NMR (200 MHz, CDCl₃): δ (ppm)=0.80–1.08 (m, 3H), 0.88 (s, 3H), 0.92(s, 3H), 1.30–1.45 (m, 3H), 1.42 (s, 3H), 1.43 (s, 3H), 1.50–1.72 (m,2H), 2.03 (tt, J=12.5, 3.1 Hz, 1H), 2.15 (s, 3H), 4.47 (d, J=15.7 Hz,1H), and 4.52 (d, J=15.7 Hz, 1H).

¹³C-NMR (50 MHz, CDCl₃): δ (ppm)=20.5, 22.2, 23.3, 23.4, 24.6, 27.0,30.7, 33.7, 39.0, 40.1, 42.1, 61.1, 87.6, 166.8, and 170.3.

EXAMPLE 12 2-[1-(3,3-dimethylcyclohexyl)-1-methylethoxy]-2-oxoethylisobutyrate

Odour: musk, ambergris-tinged, and woody.

BTD: 261° C., 0.66 mbar.

¹H-NMR (200 MHz, CDCl₃): δ (ppm)=0.80–1.12 (m, 3H), 0.88 (s, 3H), 0.92(s, 3H), 1.22 (d, J=7.0 Hz, 6H), 1.28–1.45 (m, 3H), 1.41 (s, 3H), 1.42(s, 3H), 1.50–1.75 (m, 2H), 2.05 (tt, J=12.4, 3.1 Hz, 1H), 2.65 (hep,J=7.0 Hz, 1H), 4.46 (d, J=15.8 Hz, 1H), and 4.54 (d, J=15.8 Hz, 1H).

¹³C-NMR (50 MHz, CDCl₃): δ (ppm)=18.8 (2C), 22.2, 23.3, 23.4, 24.5,27.0, 30.7, 33.6, 33.7, 39.0, 40.0, 41.9, 60.9, 87.3, 166.7, and 176.1.

EXAMPLE 13 2-[1-(3,3-dimethylcyclohexyl)-1-methylethoxy]-2-oxoethylbutyrate

Odour: weakly musk, and woody.

BTD: 274° C., 0.81 mbar.

¹H-NMR (200 MHz, CDCl₃): δ (ppm)=0.80–1.12 (m, 3H), 0.88 (s, 3H), 0.92(s, 3H), 0.98 (t, J=7,4 Hz, 3H), 1.28–1.45 (m, 3H), 1.41 (s, 3H), 1.42(s, 3H), 1.50–1.75 (m, 2H), 1.70 (sex, J=7,4 Hz, 2H), 2.04 (tt, J=12.4,3.1 Hz, 1H), 2.39 (t, J=7.4 Hz, 2H), 4.46 (d, J=15.6 Hz, 1H), and 4.54(d, J=15.6 Hz, 1H).

¹³C-NMR (50 MHz, CDCl₃): δ (ppm)=13.6, 18.2, 22.2, 23.3 (2C), 24.5,27.0, 30.7, 33.6, 35.7, 39.0, 40.0, 42.0, 60.9, 87.4, 166.7, and 172.7.

The following compounds were prepared analogously to the methodsdescribed under Example 10a, except that the alcohol component used was2-cyclohexyl-2-propanol, which can be prepared from cyclohexylmagnesiumchloride and acetone by a Grignard reaction, instead of2-(3,3-dimethylcyclohexyl)-2-propanol. Acetyloxyacetic acid, (which canbe prepared from hydroxyacetic acid and acetyl chloride, Example 14) andpropionyloxyacetic acid, (which can be prepared from hydroxyacetic acidand propionyl chloride, Example 15) were used in the esterification.Thus, only the spectroscopic data are given at this point:

EXAMPLE 14 2-(1-cyclohexyl)-1-methylethoxy)-2-oxoethyl acetate

Odour: weakly musk, and woody.

BTD: 200° C., 1.3 mbar.

¹H-NMR (200 MHz, CDCl₃): δ (ppm)=0.90–1.35 (m, 5H), 1.43 (s, 6H),1.62–1.95 (m, 6H), 2.15 (s, 3H), and 4.50 (s, 2H).

¹³C-NMR (50 MHz, CDCl₃): δ (ppm)=20.4, 23.3 (2C), 26.5, (3C), 27.2 (2C),46.4, 61.0, 87.5, 166.6, and 170.1.

EXAMPLE 15 2-(1-cyclohexyl)-1-methylethoxy)-2-oxoethyl propionate

Odour: weakly musk, and woody.

BTD: 210° C., 1.2 mbar.

¹H-NMR (200 MHz, CDCl₃): δ (ppm)=0.90–1.37 (m, 5H), 1.18 (t, J=7,5 Hz,3H), 1.43 (s, 6H), 1.62–1.95 (m, 6H), 2.44 (q, J=7,5 Hz, 2H), and 4.50(s, 2H).

¹³C-NMR (50 MHz, CDCl₃): δ (ppm)=8.9, 23.3 (2C), 26.4, (3C), 27.1, 27.2(2C), 46.5, 61.0, 87.5, 166.7, and 173.5.

EXAMPLE 16 1-cyclohexyl-1-methylethyl acetate

Triethylamine (4.6 g, 45 mmol) and 4-dimethylaminopyridine (0.40 g, 3.3mmol) are added successively to a solution of 2-cyclohexyl-2-propanol(2.1 g, 15.0 mmol), [which is obtainable from cyclohexylmagnesiumchloride and acetone by a Grignard reaction] and acetic anhydride (4.6g, 45 mmol). After stirring for 1 hour at room temperature, the reactionsolution is diluted with ether (200 ml), and the organic phase is washedtwice with 2 M HCl and twice with NaHCO₃ solution. The combined organicphases are dried over Na₂SO₄, filtered off and freed from solvent in arotary evaporator. After flash chromatography (cyclohexane/EtOAc=20:1,R_(f)=0.24) and bulb tube distillation (BTD: 120° C., 0.3 mbar) 2.3 g(83%) 1-cyclohexyl-1-methylethyl acetate is obtained as a colorless oil.

Odour: weakly musk, and woody.

¹H-NMR (200 MHz, CDCl₃): δ (ppm)=0.90–1.35 (m, 6H), 1.38 (s, 6H),1.61–1.92 (m, 5H), and 1.97 (s, 3H).

¹³C-NMR (50 MHz, CDCl₃): δ (ppm)=22.4, 23.3 (2C), 26.5 (3C), 27.3 (2C),46.1, 85.2, and 170.2.

The following compound in Example 17 was prepared analogously to themethod described under Example 16, except that propionic anhydride wasused in the esterification. Thus, only the spectroscopic data are givenat this point:

EXAMPLE 17 1-cyclohexyl-1-methylethyl propionate

Odour: weakly musk, and woody.

BTD: 125° C., 0.25 mbar.

¹H-NMR (200 MHz, CDCl₃): δ (ppm)=0.89–1.36 (m, 6H), 1.09 (t, J=7.5 Hz,3H), 1.39 (s, 6H), 1.61–1.96 (m, 5H), and 2.24 (q, J=7.5 Hz, 2H).

¹³C-NMR (50 MHz, CDCl₃): δ (ppm)=9.3, 23.4 (2C), 26.6 (3C), 27.3 (2C),28.8, 46.3, 84.8, and 173.6.

The following compounds were prepared analogously to the methoddescribed in Example 16, except that the alcohol component used was2-(3,3-dimethylcyclohexyl)-2-propanol, [which can be prepared frommethylmagnesium chloride and 1-(3,3-dimethylcyclohexyl)-ethanone by aGrignard reaction] instead of 2-cyclohexyl-2-propanol. Theesterification was carried out with acetic anhydride (Example 18) orpropionic anhydride (Example 19). Thus, only the spectroscopic data areindicated at this point:

EXAMPLE 18 1-(3,3-dimethylcyclohexyl)-1-methylethyl acetate

Odour: musk, and woody.

BTD: 125° C., 0.17 mbar.

¹H-NMR (200 MHz, CDCl₃): δ (ppm)=0.8–1.12 (m, 4H), 0.88 (s, 3H), 0.92(s, 3H), 1.22–1.42 (m, 4H), 1.38 (s, 3H), 1.39 (s, 3H), 1.62–1.76 (m,1H), and 1.97 (s, 3H).

¹³C-NMR (50 MHz, CDCl₃): δ (ppm)=22.3, 22.4, 23.3, 23.4, 24.6, 27.0,30.7, 33.7, 39.1, 40.1, 41.6, 84.9, and 170.1.

EXAMPLE 19 1-(3,3-dimethylcyclohexyl)-1-methylethyl propionate

Odour: musk, and woody.

BTD: 128° C., 0.11 mbar.

¹H-NMR (200 MHz, CDCl₃): δ (ppm)=0.8–1.13 (m, 4H), 0.88 (s, 3H), 0.91(s, 3H), 1.09 (t, J=7.5 Hz, 3H), 1.22–1.42 (m, 4H), 1.38 (s, 3H), 1.39(s, 3H), 1.58–1.76 (m, 1H), and 2.24 (q, J=7.5 Hz, 2H).

¹³C-NMR (50 MHz, CDCl₃): δ (ppm)=9.3, 22.4, 23.3, 23.4, 24.6, 27.0,28.8, 30.7, 33.7, 39.1, 40.2, 41.8, 84.6, and 173.4.

EXAMPLE 20

The present perfume oil can be used to perfume diverse cosmeticproducts.

Composition:

Ingredients Parts by weight  1. Citrophoral base (H&R) 5.0  2. AldehydeC10, 10% in BA 5.0  3. Aldehyde C11 MOA, 10% in BA 3.0  4. Farenal (H&R)3.0  5. Aldehyde C11, 10% in IPM 5.0  6. Citroxal, 50% in DEP 2.0  7.trans-Hex-2-enol, 10% in BA 2.0  8. Vertocitral (H&R) 1.0  9. Linalylacetate 45.0 10. Citrylal (H&R) 5.0 11. Mandarinal (Firmenich) 4.0 12.Lilial (Givaudan Roure) 75.0 13. Lyral (IFF) 75.0 14. Profarnesol (H&R)5.0 15. Nerolidol 5.0 16. Linalool 45.0 17. African geranium oil 5.0 18.Phenylethyl alcohol 75.0 19. Geraniol 15.0 20. Nerol 10.0 21.Hexylcinnamaldehyde alpha 50.0 22. Methyl dihydrojasmonate 15.0 23.Benzyl salicylate 100.0 24. trans,cis-2-Nonadienol, 0.1% in IPM 5.0 25.Allylionone (Givaudan Roure) 3.0 26. Isomethylionone gamma 75.0 27.Eugenol 7.0 28. Cedryl acetate 40.0 29. Sandolen (H&R) 5.0 30. Citral5.0 BA = benzyl alcohol; IPM = isopropyl myristate; DEP = diethylphthalate

The addition of

355 parts by weight 2-(1-cyclohexylethoxy)-2-methylpropyl propionate(1000 parts by weight in total) leads to a clearly discernibleharmonisation of the rose-like flowery heartnote. In addition, the fineerogenous musk note imparts an exceptional aura and increased bonding tothe present composition. In this context, the valuable character of2-(1-cyclohexylethoxy)-2-methylpropyl propionate, in particular, comesinto its own compared with compositions containing conventional muskfragrances.

55 parts by weight2-[1-(3,3)-dimethylcyclohexyl)-1-methylethoxy]-2-oxoethyl propionate(700 parts by weight in total) imparts a woody, musk note to thecomposition that is not achieved with existing musk fragrances.Furthermore, the entire composition, gains in fullness and appears morevaluable.

1. A compound of the formula (I)

where a) R¹=CH₃, R³=H or CH₃ and R² and R⁴=H, R⁵ and R⁶—independently ofone another—are H or CH₃ and Y=—CR⁷R⁸OCOR⁹, where R⁷ andR⁸—independently of one another—are H or CH₃ and R⁹ is a branched orstraight-chain C₁ to C₅ alkyl group or a branched or straight-chain C₂to C₅ alkylene group, or b) R¹ and R²—independently of one another—areCH₃ or CH₂CH₃, R³ and R⁴—independently of one another—are H or CH₃, R⁵and R⁶ together are oxygen and Y=—CR⁷R⁸OCOR⁹, where R⁷, R⁸ and R⁹ havethe abovementioned meaning, or R¹ and R²—independently of oneanother—are CH₃ or CH₂CH₃, R³ is H or CH₃, R⁴ is CH₃, R⁵ and R⁶ togetherare oxygen, and Y=R⁹, where R⁹ has the above meaning, or c) R¹ andR²—independently of one another—are CH₃ or CH₂CH₃, R³, R⁴, R⁵ andR⁶—independently of one another—are H or CH₃ and Y=—CR⁷R⁸OCOR⁹, whereR⁷, R⁸ and R⁹ have the abovementioned meaning.
 2. The compound accordingto claim 1 of the formula (IV)

where R³ and R⁴—independently of one another—are H or CH₃, R⁵ and R⁶together are oxygen, and Y=—CR⁷R⁸OCOR⁹, where R⁷, R⁸ and R⁹ have themeaning given in claim 1 or R³ is H or CH₃, R⁴ is CH₃, R⁵ and R⁶together are oxygen, and Y=R⁹, where R⁹ has the meaning given inclaim
 1. 3. The compound according to claim 1 of the formula (VI)

where R³=H or CH₃, R⁵ and R⁶—independently of one another—are H or CH₃,and Y=—CR⁷R⁸OCOR⁹, where R⁷, R⁸ and R⁹ have the meaning given inclaim
 1. 4. The compound according to claim 1, wherein said compound is2-(1-cyclohexylethoxy)-2-methylpropyl propionate,2-[1-(3,3-dimethylcyclohexyl)-1-methylethoxy]-2-oxoethyl propionate or2-[1-(3,3-dimethylcyclohexyl)-1-methylethoxy]-2-oxoethyl acetate.
 5. Amethod for the preparation of the compound according to claim 1 byreacting a substituted cyclohexylalkanol of the formula

with a) carboxylic acids of the formula

 where R¹ and R²—independently of one another—are CH₃ or CH₂CH₃, R³ andR⁴—independently of one another—are H or CH₃, R⁵ and R⁶ together arehydrogen and Y=—CR⁷R⁸OCOR⁹ where R⁷, R⁸ and R⁹ have the meaning given inclaim 1, or b) carboxylic acids R⁹—COOH or carboxylic anhydrides(R⁹—CO)₂O where R¹ and R²—independently of one another—are CH₃ orCH₂CH₃, R³ and R⁴—independently of one another—are H or CH₃, R⁵ and R⁶together are oxygen, and Y=—CR⁷R⁸OCOR⁹, where R⁷, R⁸ and R⁹ have theabove mentioned meaning, or R¹ and R²—independently of one another—areCH₃ or CH₂CH₃, R³ is H or CH₃, R⁴ is CH₃, R⁵ and R⁶ together are oxygen,and Y=R⁹, where R⁹ has the above meaning, or c) epoxides of the formula

 where R¹=CH₃, R³=H or CH₃ and R² and R⁴=H, R⁵ and R⁶—independently ofone another—are H or CH₃ and Y=—CR⁷R⁸OCOR⁹, where R⁷, R⁸ and R⁹ have theabovementioned meaning, or R¹ and R²—independently of one another—areCH₃ or CH₂CH₃, R³, R⁴, R⁵ and R⁶—independently of one another—are H orCH₃, and Y=—CR⁷R⁸OCOR⁹, where R⁷, R⁸ and R⁹ have the meaning given inclaim 1, or d) a carboxylic acid XCR⁷R⁸—COOH or a carboxylic anhydride(XCR⁷R⁸—CO)₂O in a first step and with R⁹—COOZ or (R⁹—CO)₂O in a secondstep where R¹ and R²—independently of one another—are CH₃ or CH₂CH₃, R³and R⁴—independently of one another—are H or CH₃, R⁵ and R⁶ together areoxygen, and Y=—CR⁷R⁸ OCOR⁹, where R⁷, R⁸ and R⁹ have the meaning givenin claim 1, X=halogen or OH, Z=alkali metal or H.
 6. A fragrance mixturecomprising one or more compounds according to claim 1 and a carrier. 7.A perfumed product comprising one or more compounds according to claim 1and a carrier.
 8. The compound according to claim 2 wherein R⁴=methyl.9. The compound according to claim 2 wherein R⁹=methyl, ethyl orn-propyl.
 10. The compound according to claim 3 wherein R⁵ andR⁶=methyl.
 11. The compound according to claim 3 wherein R⁹=methyl,ethyl or n-propyl.